Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
  • C08K5/3417—Five-membered rings condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene

Definitions

• the invention relates to a composition
• a composition comprising a polymer or a propylene copolymer and at least one nucleating agent capable to induce in particular the crystallization of the crystalline form ⁇ .
• olefin polymers have a structure crystalline which gives them certain mechanical and optical properties very appreciated in many industrial applications (packaging, bottles, bumpers for cars).
• the molten polymer will crystallizes on cooling in the form of spherulites, which include amorphous and crystalline domains.
• nucleating agents commonly designated nucleating agents promote the creation of additional seeds of crystallization during the cooling of a polymer.
• This increase in germs of crystallization produces a more large number of spherulites which leads to a reduction in their dimensions and increases the crystallization temperature.
• This reduction in the size of the spherulites leads to a modification of the mechanical properties: increased flexural modulus, deformation temperature under load but also embrittlement with a reduction in impact properties, especially when cold.
• nucleating agents are more particularly used in polymers or random or "block” copolymers of propylene.
• polypropylenes (homopolymer, copolymer or copo "block”) can crystallize in four forms distinct crystalline ⁇ , ⁇ , ⁇ and ⁇ , as well as in the smectic form which is obtained by quenching the molten polymer.
• the crystal form ⁇ stands out of the form a which is naturally predominant in polypropylenes by a lower melting temperature, a lower density, and a higher ductility which is interesting from the application point of view.
• ⁇ -quinacridone requires a procedure particular for dispersing the agent in the polymer and has the disadvantage of coloring the product with a pinkish tint.
• Patent application EP 0 682 066 describes the use of the salts of dicarboxylic acids, such as calcium pimelate, prepared in situ during extrusion granulation of the mixture. This way of operating requires great care to ensure the dispersion of the ingredients in the polymer. Even if a dicarboxylic acid salt is used directly, there is certainly a high proportion of crystalline form ⁇ , but the effect nucleating is quite weak. There is no significant increase in crystallization temperature and the flexural modulus decreases. In addition, we easily obtains an extrusion blow molding deposit due to the decomposition then devolatilization of part of the salt of the diacid carboxylic.
• dicarboxylic acids such as calcium pimelate
• Patent FR 2656620 relates to resin compositions polyolefins containing at least one nucleating agent chosen from the group consisting of amino acids, imido acids and pyridinequinoline acids and acridine-carboxylic. All these compounds allow to increase the crystallization temperature of the resin compositions polyolefinic containing them, and are specific nucleating agents of the ⁇ form of isotactic polypropylene.
• R 2 When x and y are> 1, the different radicals represented by R 2 can be the same or different.
• R 1 represents a hydrogen atom, a methyl radical, a is zero and A represents a divalent radical such as in which R 2 represents a hydrogen atom, a linear aliphatic hydrocarbon radical such as methyl, ethyl or propyl.
• phthaloylglycine hexahydrophthaloylglycine, naphthoylglycine, N-phthaloyl alanine, N-4-methylphthaloylglycine.
• magenium there will be mentioned magenium, calcium and barium.
• magenium it is particularly preferred to use calcium.
• the invention relates more particularly to the application of metal of group IIa of imido acids as mentioned above as ⁇ nucleating agents which increase the rate of the ⁇ crystal form polymers or copolymers of propylene.
• the calcium salt of phthaloylglycine will be used (or 1,3-dioxo 2-isoindoline acetic acid).
• the invention therefore relates to compositions comprising at least a propylene polymer or copolymer and at least one metal salt of the second group IIa of imido-acid as defined above.
• the rate of ⁇ crystalline form can be determined by DSC analysis on a PERKIN-ELMER THERMAL ANALYSIS SYSTEM instrument, by integration of the melting peaks obtained at around 155 ° C for the ⁇ form and at 165 ° C for the ⁇ form at a heating rate of + 20 ° C per minute, either after recrystallization of the sample from the molten state at a speed cooling of -10 ° C per minute, ie in primary fusion.
• the ⁇ nucleating agents of the present invention allow to obtain a rate of crystalline form ⁇ greater than 70% according to the method DSC after recrystallization of the sample from the molten state at a speed from -10 ° C / min.
• composition according to the invention also contains other additives such as pigments, stabilizers against ultraviolet rays, release agents, stabilizers against thermal degradation, lubricants, flame retardants and / or fillers, such as in particular fibers glass, anti-acid agents.
• additives such as pigments, stabilizers against ultraviolet rays, release agents, stabilizers against thermal degradation, lubricants, flame retardants and / or fillers, such as in particular fibers glass, anti-acid agents.
• the ⁇ nucleating agents according to the invention are incorporated advantageously between 0.005% and 1% and preferably between 0.025% and 0.5% by weight relative to the total weight of the polymers or propylene copolymers.
• the ⁇ nucleating agents according to the present invention can be prepared by any suitable synthesis method.
• compositions of propylene polymers or copolymers according to the invention can be prepared for example by dry mixing polymer granules or powders, one or more nucleating agents of the invention, and possibly the various additives and fillers mentioned above to room temperature for up to 1 hour.
• This dry mixing is advantageously followed by an extrusion / granulation to obtain good dispersion of the additives at a temperature can be between 170 ° C and 230 ° C then molded, for example by injection at a temperature generally of the order of 190 ° C to 250 ° C.
• the composition may advantageously contain a salt of metal from the second group IIa of fatty acid such as in particular stearate of calcium in an amount such as all of the imido acid of formula (I) introduced is salified.
• Another object of the invention is to produce compositions for polymers or copolymers of propylene comprising simultaneously with minus a metal salt of the second group IIa of the imido-acid (I) and the imidoacid (I) himself.
• compositions can advantageously be obtained according to the preferred mode which consists in carrying out, as described above, the agent nucleating ⁇ in situ with the difference that we use an amount of salt metal from second group IIa of less fatty acid so as to salify partially imido-acid (I).
• compositions according to the invention were prepared in the manner next :
• the melting temperature is reported, measured at the top of the peak, the recrystallization temperature, measured on the onset and the percentage of ⁇ form or ⁇ form obtained by integration of the melting peaks.
• T means witness.
• Tests 2 and 3 are carried out with the calcium salt of phthaloylglycine (PG 2 Ca) previously prepared.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Indole Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

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Cited By (6)

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Citations (3)

• 1998
  • 1998-06-17 EP EP98111116A patent/EP0887375A1/de not_active Withdrawn
  • 1998-06-23 CA CA002241252A patent/CA2241252A1/fr not_active Abandoned
  • 1998-06-24 JP JP10177528A patent/JPH1171487A/ja active Pending
  • 1998-06-24 CN CN98117531.7A patent/CN1210103A/zh active Pending
• 1999
  • 1999-08-02 JP JP11219345A patent/JP2000053824A/ja not_active Withdrawn

Patent Citations (3)

Non-Patent Citations (1)

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